Abstract A miniaturized polymer electrospray‐type interface is used to study metal‐ion chelation with model peptides. Taking advantage of the intrinsic electrochemical behavior of electrospray, a sacrificial electrode is used to generate at the same time electrospray and transition‐metal ions coming from the anodic dissolution of the electrode. The microspray interface provides enhanced mass transport due to its small dimensions, increasing the yield of possible reactions, in particular complex formation. Transition‐metal electrodes, e.g. copper, zinc, nickel, iron and silver, are used to obtain on‐line complexation with model peptides. It is demonstrated that the use of in‐reservoir sacrificial electrodes is an efficient way to generate metal ions in order to form and study complexes with peptides, avoiding the addition of metallic salts. Copyright © 2005 John Wiley & Sons, Ltd.